Manufacture of phenylated 6.6-diquinolyl-4.4-dicarboxylic acids and homologues.



Improvement in the Manufacture llS homologues I erases DQERH, ole cemnozr'rsmaoao, elm essences. esteem, siemem, esszesone T0 canensczqs FABRIE'. am" ecrmu veers. SGHEBING), cs seams, GERMANY.

HfiNUFAETUEE"UF PHENYLATEB *IQU "FEL'SfL- l. LBECLQEEQXYLIC ACIDS AND Hon: 931 0 i il,ll 32, 3123. Sleectiicctioe of otters Pafogniigqi .jfufiy 9 Kgflg, 110 Blowing.- Application filed February as, 1922. Serial Eo. eseace. I

' proceeds in a similar manner when toiidin and dianisidin are employed.

108 grams tolidin and 106 grams henzaldehydc are warmed in 1200 com; of ail-solute alcohol and boiled with the gradual addition oil? 88 grams of pyroracemic acid for eight hours with a reflux condenser. After standing liquor is sucked cfi while hot and the pre cipitate is boiled with alcoholic ether to purify it. The 8.8-dimethvl-6.6-diquinoly 2.2-diphenyleAi-dicaehoiylic acid obtained is a yellow powder insoluble in the usual solvents and doesnotmelt at 300 oenti rode.

(4.) 122 grains of dienisidin are mailed together with 196 grams henzaldehyde in 1200 com. of absolute alcohol with theaddi tion of 88 grams of pyroracemic acid and the product obtained purified. The 8.8-dimethoxy-6.Galiquinolyl-QQ-diphenyl i=4 clicarhoxylic acid is a brown suhstance which melts at about; 290 centig'rade and is insoluhie in the ususl solvents.

In the following claims the expression phenyleted t5.o-diquinolyl-4. i-dicarboxylic acids iricludes also the homologues of these To all whom it may concern Be it known that We, MAX Donner, doctor of philosophy, chemist, and Awesome THIELE, doctor of philosophy, chemist,'citi- Zens of the German Empire, residing, respectively, at Luisenplatz 3, Charlottcnhurg. and Bundesratsufcr 5, Berlin, Empire of Germany, have invented a new and useful of Phenylated lifl-Diquinolyl-iA-Dicarboxylic Acids and Homologucs, of which the following is l a specification.

If anilin, hcnzaldehyde and pyroracemic acid react together there is obtained as. is known 2-phenylquinolin-4-carboxylic acid.

According to this invention the phenyl- 51ted-6.6-(1iquinolyl4i-dicarboxylic acid and are obtained, it in place of 'nnilin. substituted diphenyls,. as benzidin or tolidin of dianisidin are employed. i in place of henzaldehyde, a substituted benzaldchydc is employed, the corresponding substitution product is obtained.

.Eaiamples. (1 An alcoholic solution of 65 grams of benzidin, 61 grams of pyroracemic acid and compounds. 75 grams of benzaldehyde ere boiledfor We claim es our inventien: some hours. 6.G-cliquinolyl-22-diphenyl4.4- 1. As new chemical products the phenyldicarlooxylic acid eted oil-dice]nolylee-caihoxylic acids, be- COOK COOK mg powders, insoluble in Water and in the usual organic solvents, substantially as de scribed. 2. Asset? chemical product diquinolyl-2.2-d1phenyl i.4-dicerhoxyiic sold, having the formula coca and melting at about 225 Centigrade, being" insoluble in Water and alcohol and soluble in lacial acetic acid, substantially as descri hed.

3.. Process. of menufscturihg phcnylated 5.G-diquinolyll.t-clicerhoxylic a'clds, -,which consists in ceasing substituted i I l l l J cfls// separates out. It is filtered and crystallizes froni glacial acetic acid. The new compound is of a yellowish brown color and melts at 225 centigrade; is insoluble in Water and alcohol and soluble in glacial acetic acid.

(2.) An alcoholic solution of 35 grams henzidin, 30 grams pyroracemic acid and 35 I Cali:

grams salicylaldehyde are treated in alcoholic solution as in Example 1. T e 6.6-diquinolyl 2.2 dioxyphenyl 4.4 -clicarboxylic acid is also insoluble in Water and alcohol and melts at 248 centigrade. The process cliphe'nyle,

for twenty four hours the aromatic aldehydes and pyi'm'iwelnic acid to react together and isulnting the product thus formed, substantially as described.

4. Process of. manufacturing li.(i-(li(]llill() lyl-2.2- liphenyl-4.4-clicarboxylic acid, which consists in heating an almholic solution of bon'zidin, pyt oravemic acid and benzaldehyde, and isolating the product thus formed, substantially as l0scribed.

In testimony whereof We have hereunto 10 set our signatures in the presence of two suliusci'ibing witnesses.

MAX DOHRN. ALBRECHT TIIIELE.

\Vitnesses I'IENRY IIASPER, M. REICHENBACII. 

